EP0843683B1 - Fluorosilicon compounds and preparation method - Google Patents
Fluorosilicon compounds and preparation method Download PDFInfo
- Publication number
- EP0843683B1 EP0843683B1 EP96923000A EP96923000A EP0843683B1 EP 0843683 B1 EP0843683 B1 EP 0843683B1 EP 96923000 A EP96923000 A EP 96923000A EP 96923000 A EP96923000 A EP 96923000A EP 0843683 B1 EP0843683 B1 EP 0843683B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- compound
- formula
- group
- ocf
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical class [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 title description 2
- 238000002360 preparation method Methods 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 6
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 6
- -1 vinyl siloxane Chemical class 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 150000003254 radicals Chemical class 0.000 claims description 3
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- GXGJIOMUZAGVEH-UHFFFAOYSA-N Chamazulene Chemical group CCC1=CC=C(C)C2=CC=C(C)C2=C1 GXGJIOMUZAGVEH-UHFFFAOYSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/001—Electrorheological fluids; smart fluids
Definitions
- This invention relates to fluorosilicon compounds and to a preparation method.
- fluorinated organosilicon compounds have structures in which a fluorine-containing groups such as perfluoroalkyl is bonded to a silicon atom through a dimethylene or trimethylene group. Synthesis of these compounds usually requires many stages, including a Grignard reaction and a reaction involving a precious metal catalyst, such as platinum (cf. US-A-5,202,453; EP-A-0,538,061). Reactions for making fluorinated organosilicon compounds by way of a cyclization process between olefine derivatives of silicone and fluorine have also been described (cf. US-A-2,596,967; GB-A-760,201 and GB-A-802,358; Holbrook G.W.J.
- an ER fluid comprising a solid phase dispensed in a base liquid, the latter comprising a mixture of an organosiloxane and an electrically non-conducting liquid having in its molecule at least one organofluro group.
- a fluorinated organosilicon compound having a cyclobutane ring of formula the compound being represented by the formula:- wherein R 1 ,R 2 ,R 3 and R 4 are independently selected from alkyl groups having 1 - 4 carbon atoms or independently selected from the above alkyl groups, the CF 3 CH 2 CH 2 - group, and the group, where R 6 ,R 5 ,a,b and c are as hereinafter defined.
- R 5 is a bivalent group such as -OCF 2 -, -OCF 2 CF 2 - or -OCF 2 CF(CF 3 )-.
- R 6 is a -OCF 3 - group or -F atom.
- a is an integer from 0 to 6
- b is zero or 1
- c is an integer between 2 and 6.
- Fluorinated organosilicon compounds in accordance with the invention have a wide operating temperature range and excellent chemical resistance; they are oil- and water- repellent and have outstanding dielectric properties. In addition, due to the phenomenon of "super-flexibility", the viscosity of these materials is much lower than their molecular weight would suggest. All these properties, together with their density, which can be arranged to be in the range 1.3 - 1.7 g/ml make these liquids very suitable for use as base liquids in Electro-Rheological (ER) Fluids as well as more general applications.
- ER Electro-Rheological
- the compounds are produced by a reaction between vinyl siloxane and perfluoro-olefin in the presence of a free radical inhibitor at elevated temperature and pressure.
- the ratio of reactants is in the range 1-2 moles of perfluoro-olefin for each mole of vinyl siloxane, preferably between 1.1 and 1.6.
- the reaction temperature may be in the range 150-250°C and preferably between 180 and 230°C.
- the reaction time may be 5-100 hours, and typically between 10 and 70 hours.
- the reaction is preferably carried out at elevated pressure in an autoclave.
- fluorinated organosilicon compounds prepared by this method include:-
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
Description
- This invention relates to fluorosilicon compounds and to a preparation method.
- The majority of known fluorinated organosilicon compounds have structures in which a fluorine-containing groups such as perfluoroalkyl is bonded to a silicon atom through a dimethylene or trimethylene group. Synthesis of these compounds usually requires many stages, including a Grignard reaction and a reaction involving a precious metal catalyst, such as platinum (cf. US-A-5,202,453; EP-A-0,538,061). Reactions for making fluorinated organosilicon compounds by way of a cyclization process between olefine derivatives of silicone and fluorine have also been described (cf. US-A-2,596,967; GB-A-760,201 and GB-A-802,358; Holbrook G.W.J. Am.Chem.Soc 82, 825 (1960); Park J.D. J.Org.Chem., 25, 1628 (1960). However, this reaction has been largely ignored over the past ten years. In EP-A-0589637 is described an ER fluid comprising a solid phase dispensed in a base liquid, the latter comprising a mixture of an organosiloxane and an electrically non-conducting liquid having in its molecule at least one organofluro group.
- According to the first aspect of the invention there is provided a fluorinated organosilicon compound having a cyclobutane ring of formula :the compound being represented by the formula:-
wherein R1,R2,R3 and R4 are independently selected from alkyl groups having 1 - 4 carbon atoms or independently selected from the above alkyl groups, the CF3CH2CH2- group, and the
group, where R6,R5,a,b and c are as hereinafter defined. R5 is a bivalent group such as -OCF2-, -OCF2CF2- or -OCF2CF(CF3)-. R6 is a -OCF3- group or -F atom. a is an integer from 0 to 6, b is zero or 1, c is an integer between 2 and 6.
- Fluorinated organosilicon compounds in accordance with the invention have a wide operating temperature range and excellent chemical resistance; they are oil- and water- repellent and have outstanding dielectric properties. In addition, due to the phenomenon of "super-flexibility", the viscosity of these materials is much lower than their molecular weight would suggest. All these properties, together with their density, which can be arranged to be in the range 1.3 - 1.7 g/ml make these liquids very suitable for use as base liquids in Electro-Rheological (ER) Fluids as well as more general applications.
- According to a second aspect of the invention, there is provided a method of manufacturing a compound in accordance with the first aspect by reacting a vinyl siloxane of general formula:-wherein R1,R2,R3,and R4 have the meanings defined above, with a perfluoro-olefin of the general formula:-
- The compounds are produced by a reaction between vinyl siloxane and perfluoro-olefin in the presence of a free radical inhibitor at elevated temperature and pressure.
- Preferably, in the cyclization reaction of the vinylsiloxane and the perfluoro-olefin, the ratio of reactants is in the range 1-2 moles of perfluoro-olefin for each mole of vinyl siloxane, preferably between 1.1 and 1.6. The reaction temperature may be in the range 150-250°C and preferably between 180 and 230°C. The reaction time may be 5-100 hours, and typically between 10 and 70 hours. The reaction is preferably carried out at elevated pressure in an autoclave.
- Typical examples of fluorinated organosilicon compounds prepared by this method include:-
Claims (10)
- A fluorinated organosilicon compound having a cyclobutane ring of formula:-the compound being represented by the formula:-
wherein R1,R2,R3 and R4 are independently selected from alkyl groups having 1-4 carbon atoms, the CF3CH2CH2- group, and the
group, R5 is a bivalent group selected from -OCF2-, -OCF2CF2-, or -OCF2CF(CF3)-, R6 is a CF3O- group, or F- atom attached to a carbon atom of the R5 group, a is an integer from 0 to 6, b is zero or 1, and c is an integer between 2 and 6.
- A compound as claimed in Claim 1, having the formula:-
- A compound as claimed in claim 1 having the formula:-
- A compound as claimed in claim 1 having the formula:-
- A method of manufacturing a compound as defined in any preceding Claim by reacting a vinyl siloxane of general formula:-wherein R1,R2,R3, R4 and a are as previously defined, with a perfluoro-olefin of general formula:-
- A method as claimed in Claim 5, wherein the ratio of reactants is in the range 1 - 2 moles of perfluoro-olefin for each mole of vinyl siloxane, preferably between 1.1 and 1.6.
- A method as claimed in Claim 5 or 6, wherein the reaction is carried out at a temperature range 150-250°C and preferably between 180 and 230°C
- A method as claimed in any one of Claims 5 to 7, wherein the reaction is carried out over the time period of 5-100 hours, and preferably between 10 - 70 hours.
- A method as claimed in any one of Claims 5 to 8, wherein the reaction is carried out at elevated pressure.
- An electro-rheological fluid having, as its base liquid, a compound as defined in any one of Claims 1 to 4.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB9514104.0A GB9514104D0 (en) | 1995-07-11 | 1995-07-11 | Novel fluorosilicon compounds and methods of preparing them |
| GB9514104 | 1995-07-11 | ||
| PCT/GB1996/001644 WO1997003078A1 (en) | 1995-07-11 | 1996-07-10 | Fluorosilicon compounds and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0843683A1 EP0843683A1 (en) | 1998-05-27 |
| EP0843683B1 true EP0843683B1 (en) | 2001-02-14 |
Family
ID=10777450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP96923000A Expired - Lifetime EP0843683B1 (en) | 1995-07-11 | 1996-07-10 | Fluorosilicon compounds and preparation method |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5948929A (en) |
| EP (1) | EP0843683B1 (en) |
| JP (1) | JPH11509198A (en) |
| AU (1) | AU6366696A (en) |
| DE (1) | DE69611791D1 (en) |
| GB (1) | GB9514104D0 (en) |
| WO (1) | WO1997003078A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6494884B2 (en) * | 2001-02-09 | 2002-12-17 | Concentric Medical, Inc. | Methods and devices for delivering occlusion elements |
| KR100553327B1 (en) * | 2003-11-18 | 2006-02-20 | 광주과학기술원 | Siloxane monomers containing trifluorovinylether group, sol-gel hybrid polymers prepared by using the siloxane monomers |
| JP2007276656A (en) * | 2006-04-07 | 2007-10-25 | Nippon Sheet Glass Co Ltd | Vehicular window glass |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2596967A (en) * | 1948-11-19 | 1952-05-20 | Westinghouse Electric Corp | Fluorine-containing organosilicon compounds |
| DE1047439B (en) * | 1953-12-21 | 1958-12-24 | Dow Corning | Process for the production of new fluorine-containing organopolysiloxanes |
| JPH0662647B2 (en) * | 1988-02-12 | 1994-08-17 | 信越化学工業株式会社 | Fluorine-containing organosilicon compound |
| JPH0778066B2 (en) * | 1991-10-17 | 1995-08-23 | 信越化学工業株式会社 | Fluorine-containing organosilicon compound and method for producing the same |
| EP0589637B1 (en) * | 1992-09-21 | 1997-06-04 | Dow Corning Corporation | Improved electrorheological fluid formulations using organosiloxanes |
-
1995
- 1995-07-11 GB GBGB9514104.0A patent/GB9514104D0/en active Pending
-
1996
- 1996-07-10 EP EP96923000A patent/EP0843683B1/en not_active Expired - Lifetime
- 1996-07-10 DE DE69611791T patent/DE69611791D1/en not_active Expired - Lifetime
- 1996-07-10 WO PCT/GB1996/001644 patent/WO1997003078A1/en active IP Right Grant
- 1996-07-10 US US08/981,980 patent/US5948929A/en not_active Expired - Fee Related
- 1996-07-10 AU AU63666/96A patent/AU6366696A/en not_active Abandoned
- 1996-07-10 JP JP9505604A patent/JPH11509198A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| US5948929A (en) | 1999-09-07 |
| EP0843683A1 (en) | 1998-05-27 |
| DE69611791D1 (en) | 2001-03-22 |
| WO1997003078A1 (en) | 1997-01-30 |
| GB9514104D0 (en) | 1995-09-13 |
| JPH11509198A (en) | 1999-08-17 |
| AU6366696A (en) | 1997-02-10 |
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